ES2206564T3 - OIL FOR AGRICULTURAL USE. - Google Patents

Abstract

AN OIL FOR AGRICULTURAL USE IS DEFINED TO WHICH A BASIC OIL SOLUBLE COMPOUND OR A SOLUBLE OIL UV DEACTIVATOR IS ADDED. PREFERIBLY THE BASIC COMPOUND IS: (A) A SULFONATE; (B) A FENATE; (C) A COMPOUND CONTAINING HYDROXY; AND / OR (D) AN AMINA. PREFERIBLY THE UV DEACTIVATOR IS: (A) A UV ABSORBENT; AND / OR (B) A FREE RADICAL RECEIVER OR REMOVAL.

Description

Oil for agricultural use.

Field of the Invention

The present invention relates to an oil for use in agriculture, in particular an oil derived from oil for "PSO" nebulizers, being mainly a oil to use as an insecticide and / or a mist oil acaricidal control More particularly, the invention relates to a PSO with certain additives that reduces the phytotoxicity of the oil in relationship with, for example, crops and plants. The invention is will describe mainly in relation to its use with oils refined and semi-refined, but it should be appreciated that The invention has a wider application.

Background Technique

Oil fogging oils ("PSO") are used in agriculture alone and as vehicles or solvents for nebulizing pesticides, herbicides, micronutrients, chemical adjuvants, etc. Oils are widely used for their efficacy in controlling a wide range of pests and diseases, and for its relatively low cost, relatively low danger for health (including low toxicity in mammals) and its broad availability. They also show an absence of residual effect against beneficial predators and parasitoids.

However, certain qualities and applications of PSOs have been shown to be phytotoxic, particularly in applications with high dosages, or in environments where the Sunlight exposure is imminent or intense. Phytotoxicity acute can lead to excessive leaf fall in plants and to less obvious chronic symptoms such as inhibition of crop production.

There has been much debate in the literature scientific about how oil mechanisms induce phytotoxicity, but a primary source of phytotoxicity to membrane rupture. Membrane rupture involves dissolving the semipermeable membrane of the leaves, which leads to a break in the structure of the plate and / or death of the plant. The problem of membrane rupture was greatly overcome measure with the improvement of oil refinement and the instigation of Quality criteria

Phytotoxic effects have been related to distillation temperature or viscosity of the particular oil used in fogging. Phytotoxicity has also been attributed at the dosing rate of the nebulizer oil and at the duration of fogging.

However, researchers and manufacturers in this area have overlooked the photodegradation of modern PSO very refined with subsequent phytotoxicity.

Acid formation in PSOs is associated with photodegradation (eg oxidation) of PSO mediated with UVA radiation. At present it is assumed that a contributing or main factor in the phytotoxicity of PSO could be related to the level of acidity of the PSO when nebuliza, or the one that develops after the nebulización. Even "superior" nebulization oils (ie oils from highly refined nebulization), when exposed to light, can develop acidity and become remarkably phytotoxic. Is trend can be improved when an oil applied to a plant is exposed to UV radiation (for example sunlight) during a period of prolonged time, so that many of the oil components they photo-oxidize in organic acids, attacking their Once to the plants.

US4125400 describes an oil of fogging for agriculture that includes a compound antioxidant JP57-175109 describes a purified machine oil that includes a UV absorbing agent. Document DS33771281 describes an oil composition lubricant that includes a basic metal sulphonate alkaline earth. EP225580 describes a composition of lubricating oil that includes a copper-based composition that It contains a metal. US5439602 describes a sulphonate overweight combined with petroleum oxidates for formation of metals. Document DS4165230 describes fogging oils for agriculture containing zinc dialkyl dithiophosphates. Document EO312313 describes a sulfonate composition Overweighted metal as an additive to a lubricating oil.

It would be advantageous that at least the embodiments preferred of the present invention provide an oil to use in agriculture, in particular an oil for fogging in the agriculture, which includes a component, or components, capable of prevent the formation of acid products in the oil, or improve or Neutralize its effects.

Summary of the invention

The present invention provides an oil of fogging in agriculture with lower phytotoxicity when applies to a crop or plant, including in it an agent of UV absorption which is:

(a) a benzoxazole or benzothiazole compound excluding the compound 2-mercaptobenzothiazole; or

(b) the compound:

(i) 2- (2H-benzotriazol-2-yl) -3-methyl-6-dodecyl phenol; or

(ii) propionate of iso-octyl-3- (3- (2H-benztriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl.

Particular embodiments of the invention will be describe and claim in the appended claims.

As described above, the exposure of a PSO at UV radiation causes photo-degradation of the PSO (that is, by photo-oxidation of the same) in peroxides, acids, esters, polymers etc, increasing from this forms the phytotoxicity of the PSO. This way you can prevent or improve photo-oxidation with the compounds of UV absorption, which absorb UV radiation from the photo-oxidation

The UV absorbing agent in (i) is commercially available as TINUVIN 171 and is present preferably 0.005% by weight of the total oil (TINUVIN 171 is a registered trademark of Ciba Geigy).

The UV absorbing agent in (ii) is commercially available as TINUVIN 384 (registered trademark of Ciba Geigy) TINUVIN 1871 and 384 are UV absorption agents liquids, being 384 of the hydroxyphenyl benztriazole class. The TINUVIN 384 has high thermal stability and permanence.

Preferably, the propionate of iso-octyl-3- (3- (2H-benztriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl It is present in the range of 0.001-0.5% by weight of the oil, more preferably in an amount of about 0.01% by weight of the oil.

A preferred oil to use as PSO is a Refined light oil (hydrocarbon chain length of C 13 to C 35). In particular, it is preferred that the portion of PSO oil is a light paraffinic or light naphthenic oil petroleum derivative from C 15 to C 35.

Preferably, the light paraffinic oil or Light naphthenic is:

(a) chemically neutralized;

(b) treated with clays;

(c) solvent refining; or

(d) hydro-treated.

The physical properties of such oils are shown in Tables 2 and 3.

Misting oil for agriculture may additionally include a soluble basic compound in the oil that is an overweight sulfonate or a phenate overweight Using such an oil-soluble basic compound, it is they can neutralize at least some of the acidic compounds present or formed in the oil in use.

Preferably, the sulfonate overweight in an overweight calcium sulfate. Preferably, the sulphonate Overweighted calcium is present in the oil at an interval 0.01-5% by weight of the total. It is more preferred than the overweight calcium sulphonate is present in the oil in an amount of approximately 1.0% by weight of the total.

An overweight metal sulphonate includes a aqueous mycelium defined by a variety of chain molecules of relatively long hydrocarbons with a polar head (i.e. sulfonate functionality) and a hydrophobic tail (for example, a long chain alkyl) and an excess amount of metal base (for example, calcium carbonate) in the micel. (Figure 5 shows shows an illustration of an overweight sulfonate). I also know they can use metals other than calcium in the sulphonate overweight or overweight phenate (for example sulfonates overweight magnesium).

Normally, surfactants are added to the PSO to allow the oil to disperse in water for fogging later. Surfactants include nonionic surfactants. The nonionic surfactants can be added in the range of 0.5% in 20% weight by weight.

In a spray oil formulation preferred, a light refined oil may include 0.5-20% by weight of non-ionic surfactant, 1.0% in weight of sulfonate overweight in calcium and 0.005% by weight of benztriazole compound. In this way, the formulations Preferred may include a UV absorbing agent and a basic compound soluble in oil.

In a further aspect of the present invention there is provided an additive composition for an oil for use in agriculture which may include a UV absorbing agent (as defined above) and optionally a base (as defined above). This additive composition also includes emulsifying surfactant (s) (as defined above). The additive composition can be provided separately from the oil (for example PSO) and can be added to the oil in situ (for example, before fogging). The additive composition finds a useful application when added to less refined oils than ideal, or oils that are in different stages of oxidation, and can stabilize, eliminate or reduce the phytotoxicity of such oils before fogging, etc.

Brief description of the drawings

The forms will be described below. preferred of the invention, by way of examples, and together with the attached figures in which:

Figure 1 shows the effect of acidity on the Betacyanine efflux and control thereof by adding sulfonate overweighted calcium to oil (with reference to oils without such addition);

Figures 2 and 4 show the effect of adding a base and a UV absorbing agent to different oils when exposed to UV radiation;

Figure 3 shows a measure of the transform fourier of the carbonyl infrared peak (i.e. a measure acidity) for different oils with a base and / or an agent of UV absorption added thereto;

Figure 5 schematically shows structures typical molecular sulphonates and phenates.

Figure 6 schematically shows the TINUVIN 384 molecular structure; Y

Figure 7 shows the transmission spectrum of different concentrations of TINUVIN 384 solutions in toluene

Ways to carry out the invention

The embodiments will be described below. Preferred of the invention.

Examples

A conventional nomenclature has been used in All examples for oil mist oils. By example, when a PSO is referred to as a 60N oil or 70N, the part of the number is referred to and derived from the measure of viscosity in universal seconds Saybolt and the neutral term (N) It refers to the paraffinic nature of the oil.

When ASTM and AS terminology is used in this Descriptive report is a reference to the American Society for Testing and Materials and the Australian Standard, respectively.

The rupture of the membrane (and therefore phytotoxicity), as they are called in the Figures, has been measured by the Betacyanine Efflux Test. The conventional test was applied in beet disks without cuticle and in this way you can directly control the effects of a PSO on the membrane of the cell.

Rupture of the membrane by efflux of betacyanin in membranes of unprotected cells

The oil-induced rupture of membranes cells not protected by a cuticle layer was measured with the Betacyanine efflux in beet disks (Coupland, D. et al (1989). Evaluation of three techniques used to determine surfactant phytotoxicity; Annals of Applied Biology 115, 147-156). The test material was prepared by doing 7 mm diameter discs with a cork saw and cutting them with a thickness of 1 mm. Preliminary studies showed that discs were best used after a two hour rinse in water of the tap followed by air drying. It was essential to remove the water absorbed since the water induced a premature efflux of betacyanine

Dry discs were added (n-3) of known fresh weight to 10 ml test tubes and covered completely with 2 ml of oil. Then the treatments are incubated for 3 hours at 30 ° C, after which a 5 ml isotonic solution of 0.4M sorbitol in deionized water. The tubes were set aside to allow the efflux of betacyanin for 18 hours at 20 ° C. The analysis of the aqueous layer was performed by analysis colorimetric at 535 nm in 1 cm cells against a solvent White. Then, absorbency readings were normalized to absorbency / disc weight to eliminate differences between discs. This procedure along with the selection of three discs randomly selected was satisfactory in obtaining of reproducible results. The preparation of the disks for produce a maximum efflux for normalization purposes did not improve precision

The pink color developed with the efflux of betacyanine adjusted to a classic logistic curve when it calibrated with the acidity of the oil. The effective dose (ED 50) for 3 hours of contact was 0.11 mg KOH / g oil (ASTM D927) and the detection limit for an unobservable effect was 0.08 mg KOH / g oil (0.5 units of Abs / g).

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In the Figures and Tables, the phytotoxicity of different fogging oils, determined by the efflux of betacyanin.

In the tests, it was established that when a exceeded a membrane rupture value of 0.5 Units of Absorbency / g specimen (Abs / g), damage to the plant would occur. In other words, a result of 0.5 or less is a value of Phyto-secure membrane rupture.

Example 1 (Figure one)

Different levels of sulfonate were added overweighted calcium (shown as "base" in Figure 1) to 70N and 150N oils, oxidized and non-oxidized. As shown clearly in Figure 1, with the addition of 0.1% base and 1% of base, the membrane rupture value is kept below approximately 0.4 Abs / g (which is in the area phyto-safe). Figure 1 also compares these oils versus conventional oils with different values of acidity.

Examples 2 (Figure two)

A 70N oil had various additives (as is shown in Figure 2) incorporated therein. Figure 2 shows the effect of exposing the oil to 4 mW / cm2 of radiation UV / cm2 versus time, and also indicates the effect of variation in base levels (overweight sulfonate of calcium) and UV absorption agent (TINUVIN 384).

Example 3 (Figure 3)

A 70N oil was exposed (with additives similar to those of Example 2) at 4 mW of UV radiation / cm2. Figure 3 shows the results as a spectrum fourier transform infrared oil versus time, indicating the variation in the acidity between different "treated" and "untreated" oils. In Figure 3, it can be seen that even the addition of a Small amount of base and UV absorbing agent minimizes the acid formation (indicated by carbonyl function, that is, absorbency at 1710 cm -1).

Example 4 (Figure 4)

In a manner similar to Example 2, incorporated the additives referred to in the Figure 4 to a 70N oil and then exposed to UV radiation. It shows the acidity of the resulting oil over time for different combinations of base and UV absorbing agent, indicating that they get excellent results when both the base are present as the UV deactivator.

Example 5

Additive compositions were prepared for use as a different additive or a concentrated set to add to oils for use in agriculture. Additive compositions normally included one or two nonionic surfactants (i.e. emulsifying surfactants to make the oil suitable for use as PSO (in water)), a UV absorbing agent (TINUVIN 384) and optionally an oil soluble base (overweight sulfate of calcium).

An advantage of the additive composition is that it can be added to the PSO in situ (that is, it can be transported in concentrated form to the PSO user, who then adds it in an appropriate dosage). This means that a local or regional oil can be used (that is, the treated oil does not have to be transported to the place of application) and therefore transport costs can be reduced.

A preferred additive composition was the next: Non-ionic surfactant (s) plus sulfate overweighted calcium and benztriazole compound in a ratio of 140.5: 1, (not including the surfactant).

Example 6

Another preferred formulation for an oil of light oil mist included 0.5-20% in weight of non-ionic surfactant, 1.0% by weight of sulphonate overweighted calcium and 0.05% by weight of TINUVIN 384.

Table 1 summarizes below the photo-degradation of different compositions when added to a 60 Neutral oil, 70 Neutral oil and 150 oil Neutral, fronts to these oils alone. This Table demonstrates the broad applicability of the formulation in different types of oils, and shows that membrane rupture and acidity is reduced considerably when such additives are present.

Table 2 shows the chemical characteristics typical of oil mist oils suitable for use with the present invention. Table 3 shows some of the properties of a wide range of light oils of nebulization suitable for use in the present invention.

Figure 5

Figure 5 shows a representation schematic of the typical molecular structures of sulphonates and overweight phenates, in which the mycelium is defined by a diversity of groups with soluble polar sulfate functionality in water (hydrophilic heads) facing inwards, having each head sulfonate an oil-soluble non-polar alkyl chain (tail hydrophobic) that projects outwards.

Overweighted sulfonates contain a excess amount of metal base (for example, carbonate of calcium) that neutralizes acids formed during photodegradation of oils. The length of the alkyl chain varies from 18 to more than 20 carbon atoms, while the length of the alkyl chain of the phenates contains approximately 12 carbon atoms

Figures 6 and 7

Figure 6 shows the chemical structure of TINUVIN 384 and Figure 7 shows a transmission spectrum for different concentrations of TINUVIN in toluene, indicating its use preferred as UV absorbing agent.

With the above description, you can see that the addition of an oil soluble base and a UV deactivator oil soluble (in different preferred configurations) can eliminate, improve or reduce membrane rupture (measured by the betacyanin efflux) and acidity in nebulization oils of oil (as a result of the photo-degradation / photo-oxidation of nebulization oils in the presence of oxygen and UV radiation), reducing therefore the phytotoxicity of the oils of fogging

The invention finds application in a wide diversity of fogging oils, and particularly with oils refined base less than ideal. In this way, by adding a preferred composition to such unrefined mist oils Ideally, they can be used immediately with a lower risk of phytotoxicity

TABLE 1 The effect of additives in fogging oils of Petroleum

one

two

3

A = 70 Neutral

B = Proposed Australian Standard (Furness et al. 1987) .These classes correspond to oil quality "superior" in the USA.

C = Carbon Number when X% has been distilled of the dough

NR = Narrow Interval

% Cp =% carbon atoms as paraffin, n = naphthalene, a = aromatic.

DT = distillation temperature (C a: @ 101 kPa ASTM D2887 or 10 kPa ASSTM D1160).

TABLE 3

4

A: US EPA (1978) TSCA, control act of U.S. toxic substances

B: CAS number: service registration number Chemical summaries

Claims (24)

1. A fogging oil for agriculture with less phytotoxicity when applied to a crop or plant, having a UV absorbing agent incorporated therein oil soluble which is: (a) a benzoxazole or benzothiazole compound excluding the compound 2-mercaptobenzothiazole; or (b) the compound: (i) 2- (2H-benztriazol-2-yl) -3-methyl-6-dodecyl phenol; or (ii) propionate of iso-octyl-3- (3- (2H-benztriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl. 2. A fogging oil for agriculture as claimed in claim 1 wherein the compound (ii) is present in the range of 0.001-0.5% in total weight 3. A fogging oil for agriculture as claimed in claim 2 wherein the compound (i) is present in approximately 0.1% by weight of the total. 4. A fogging oil for agriculture as claimed in any one of claims 1 to 3, in which the oil part is an oil derived from petroleum C 15 to C 35 light paraffinic or light naphthenic. 5. A fogging oil for agriculture as claimed in claim 4, wherein the oil Light paraffinic or light naphthenic is: (a) chemically neutralized; (b) treated with clays (c) solvent refining; or (d) hydro-treated. 6. A fogging oil for agriculture as claimed in any one of claims 1 to 5, additionally including an oil soluble basic compound that It is an overweight sulfonate or an overweight phenate. 7. A fogging oil for agriculture as claimed in claim 6, wherein the sulfonate Overweighted is an overweighted calcium sulphonate. 8. A fogging oil for agriculture as claimed in claim 7 wherein the sulfonate of overweight calcium is present in the oil at an interval 0.01-5.0% by weight of the total. 9. A fogging oil for agriculture as claimed in claim 8, wherein the sulfonate of overweight calcium is present in the oil at an interval of approximately 1.0% by weight of the total. 10. A fogging oil for agriculture as claimed in any one of claims 1 to 9, which also includes surfactant (s) emulsifier (s). 11. A fogging oil for agriculture as claimed in claim 10, wherein the Surfactants are nonionic surfactants and are added from approximately 0.5% to 20.0% by weight of the total. 12. An additive composition of an oil of fogging for agriculture, including in the composition a UV absorption agent as defined in any of the claims 1 to 3 and emulsifying surfactants. 13. An additive composition as claimed in claim 12 additionally including a compound oil soluble base as defined in any of the claims 6 to 9. 14. An additive composition as claimed in claim 12 or in claim 14 which is added to a oil as defined in claim 4 or claim 5. 15. An additive composition as claimed in any of claims 12 to 14 wherein emulsifying surfactants are as defined in the claim 11. 16. The use of a fogging oil that has incorporated therein a soluble UV absorption agent in oil that is: (a) a benzoxazole or benzothiazole compound excluding the compound 2-mercaptobenzothiazole; or (b) the compound:

(i) 2- (2H-benztriazol-2-yl) -3-methyl-6-dodecyl phenol; or

(ii) propionate of iso-octyl-3- (3- (2H-benztriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl.

17. The use of a fogging oil for agriculture as claimed in claim 16, wherein the oil part is an oil derived from C15 oil at C 35 light paraffinic or light naphthenic. 18. The use of a fogging oil for agriculture as claimed in claim 16 or 17, in which light paraffinic or light naphthenic oil is: (a) chemically neutralized; (b) treated with clays (c) solvent refining; or (d) hydro-treated. 19. The use of a fogging oil for agriculture as claimed in any of the claims 16 to 18, further including a compound basic oil soluble which is an overweight sulfonate or a overweight phenate. 20. The use of a fogging oil for agriculture as claimed in claim 19, wherein the overweight sulfonate is a calcium sulphonate overweight 21. The use of a fogging oil for agriculture as claimed in claim 20 wherein the overweight calcium sulphonate is present in the oil in a range of 0.01-5.0% by weight of the total. 22. The use of a fogging oil for agriculture as claimed in claim 21, wherein the overweight calcium sulphonate is present in the oil in a range of approximately 1.0% by weight of the total. 23. The use of a fogging oil for agriculture as claimed in any of the claims 16 to 22, further including surfactant (s) emulsifier (s). 24. The use of a fogging oil for agriculture as claimed in claim 23, wherein the surfactants are nonionic surfactants and are added in approximately 0.5% to 20.0% by weight of the total.